US3502636A - Solution polymerization of isoprene with aluminium trialkyl titanium tetrachloride catalyst activated by ethers and halogenated alkanes - Google Patents

Solution polymerization of isoprene with aluminium trialkyl titanium tetrachloride catalyst activated by ethers and halogenated alkanes Download PDF

Info

Publication number
US3502636A
US3502636A US532587A US3502636DA US3502636A US 3502636 A US3502636 A US 3502636A US 532587 A US532587 A US 532587A US 3502636D A US3502636D A US 3502636DA US 3502636 A US3502636 A US 3502636A
Authority
US
United States
Prior art keywords
isoprene
polymerisation
catalyst
ethers
aluminium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US532587A
Other languages
English (en)
Inventor
Josef Witte
Gottfried Pampus
Nikolaus Schon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Application granted granted Critical
Publication of US3502636A publication Critical patent/US3502636A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/08—Isoprene

Definitions

  • isoprene can be polymerised with organometallic mixed catalysts of aluminium trialkyls and titanium (IV) chloride to give polyisoprene in which the monomer units are'linked by 1,4-cis-bonds. It is possible by this process to obtain a polyisoprene which is similar in many respects to natural rubber.
  • halogen alkanes are preferably chloro alkanes and bromalkanes with 1 to 6 carbon atoms which carry at least two ch10- rine or bromine atoms on the same or on adjacent carbon atoms.
  • a process for the solution polymerisation of isoprene in organic solvents by means of a catalyst comprising titanium tetrachloride and an aluminium trialkyl has now been found which comprises preparing the catalyst from the titanium compound and the aluminium trialkyl in the presence of 0.05 to 5 moles of an ether, per mole of aluminium trialkyl, and adding to the polymerisation solution, 0.05 to 50 moles, per mole of titanium compound, of an alkane carrying at least two halogen atoms on the same or on adjacent carbon atoms.
  • halogen atoms are preferably chlorine and bromine atoms.
  • ethers for use in the process according to the invention include open-chained aliphatic ethers such as di-n-butyl ether and diisoamyl ether; polypropylene oxide of low molecular weight and, finally, aromatic or mixed aliphatic-aromatic ethers, such as diphenyl ether or anisole.
  • Aluminium trialkyls whose alkyl groups contain from 2 to 6 carbon atoms, are mainly suitable for use as the aluminium trialkyls. Aluminium triethyl and aluminium triisobutyl are preferably used.
  • Aromatic or aliphatic hydrocarbons for example, benzene toluene, hexane, iso-octane or cyclohexane, can be used as the solvents.
  • Suitable halogenohydrocarbons carrying at least two chlorine or bromine atoms on the same or on adjacent carbon atoms include, for example, 1,1-dichloroethane, 1,2-dichloroethane, dibromomethane, 1,2-dibromomethane, 1,1,2-tribromoethane, 1,2-dichloroand 1,2-dibromoethane and, preferably, 1,l,2,2,-tetrachloroethane and l,1,2,2-tetrabromoethane, or chlorine and bromine containing compounds, for example, 1,2-dichloro-l,2-dibromoethane.
  • Polymerisation may be carried out either continuously or batchwise.
  • the aluminium trialkyl is initially added to the solvent-monomer mixture, followed by the ether, the halogenoalkane and finally by the titanium (IV) chloride. It is important firstly that the catalyst should be prepared in the presence of monomeric iso'prene, and secondly that the aluminium trialkyl and the ether are reacted together before the titanium (IV) chloride is introduced.
  • a mixture of solvent and isoprene is initially introduced into a polymerisation vessel. 0.5 to 5,
  • the halogenohydrocarbon is then added, followed by the titanium (IV) chloride which is added in such a quantity that the molar ratio of aluminium to titanium compound is from 0.9:1 to 1.25: 1.;
  • the quantity in which the halogenoalkane is added is dependent upon the type of; compound used, and may be from 0.05 to 50 moles per mole of titanium (IY) chloride.
  • the catalyst may also be prepared in a part of the solvent-monomer mixture by adding the components in the aforementioned order, ageing thezresulting mixture at to 50 0., preferably at 15 to 30 C. and adding it to the remainder of the solvent-isoprene mixture.
  • Polymerisation which may take from 2 to 8 hours is carried out at temperatures in the range from 5 to 50 C., preferably in the range from 0 to 30' C.
  • a sufiicient quantity of a lower aliphatic alcohol such'as ethanol or isopropanol, or an organic acid, such as stearic acid or disproportionated resin acid, may be added in order to destroy the catalyst.
  • the conventional s'tabilisers such as, for example; 2,6-di-tert.-butyl-4-methylphenol, may be used. 7
  • the polymer may be isolated by precipitation with a lower" aliphatic alcohol or, in a preferred embodiment, by distilling off the solvent with'steam.
  • the polymers obtained by the process according to the invention are polyisoprenes, at least 80% and, in most instances, 95 to 98% of whose double bonds have the cis-.1,4-configuration.
  • Example 1 1500 ml. of n-hexane and'240 g. of isoprene are introduced, in the absence of air and moisture, into a vessel equipped with stirring mechanism. 0.77 g. of aluminium triethyl and 0.2 g. of di-n-butyl' ether are then added with stirring. After this mixture has been thoroughly stirred, 1.6 g. of 1,1,2,2-tetrachloroethane are added,
  • Example 2 The procedure of Example 1 was repeated for Examples 2 to 6 which are summarised in Table 1. Examples 2, 7 and 8. are comparison tests: '5
  • Example 9 The procedure of Example 1 was repeated for Examples 9 to 12. The details are set out Table 2. Examples 9 and 1 1 are comparison tests.
  • Example No 9 10 .1 12 n-Hexane (ml) 1, 500 1', 500 1, 500 1, 500 Isoprene (g.).... 200 200 200 A1 01H5)3 (g) 0.63 0, 63 0. er. molumo (g.)----. 0.17 0.17 Cl2CHOHC1g (g. s 1. s CH2CICHzCi (g. 3. 2 a. 2 'rioju (g.) 0.892 7 0. 892 0, 892 0. sa2
  • Example 19 the polyrnerisationtemperature was 30 C.
  • Example 23 is a comparison test.
  • Example N o 23 24 25 n-Hexane (ml) 1, 500 1, 500 1, 500 Isoprene (g)... 200 200 200 Al (021-193 (g.) 0. 64 0. 64 0. 64 Isa-(014E020 (g) 0.51 1.02 BrgCHCHBfz (g). 0.3 0.3 0.3 TiCh (g.) 0. 892 0. 982 0. 892 Polymerisation temp. C.) 25 25 25 25 25 25 25 Polymerisation time (hours) 5 5 5 5 Yield (percent) 70 88 42 ML-4 /100 C 61 55 Examples 26-30 The procedure of Example 1 was repeated for Examples 26 to 30. The details are set out in the following table. Examples 26 and 27 are comparison tests.
  • a process for producing polyisoprene having predominantly 1,4-cis-linkages which comprises polymerizing isoprene while dissolved in a hydrocarbon solvent containing an aluminium trialkyl-titanium tetrachloride catalyst activated by 0.05 to 5 moles of an ether, per mole of aluminium trialkyl, and 0.05 to 50 moles, per mole of titanium compound, of an alkane carrying at least two halogen atoms on the same or on adjacent carbon atoms.
  • a catalyst composition prepared by adding to a solution of isoprene in a hydrocarbon solvent therefor, aluminium triethyl, di-n-butyl ether, a polyhalogenoethane, and TiCl the aforesaid componentsbeing added to the solution in the order set forth above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
US532587A 1965-05-24 1966-03-08 Solution polymerization of isoprene with aluminium trialkyl titanium tetrachloride catalyst activated by ethers and halogenated alkanes Expired - Lifetime US3502636A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF46132A DE1253917B (de) 1965-05-24 1965-05-24 Verfahren zur Loesungspolymerisation von Isopren

Publications (1)

Publication Number Publication Date
US3502636A true US3502636A (en) 1970-03-24

Family

ID=7100856

Family Applications (1)

Application Number Title Priority Date Filing Date
US532587A Expired - Lifetime US3502636A (en) 1965-05-24 1966-03-08 Solution polymerization of isoprene with aluminium trialkyl titanium tetrachloride catalyst activated by ethers and halogenated alkanes

Country Status (6)

Country Link
US (1) US3502636A (en:Method)
BE (1) BE681438A (en:Method)
DE (1) DE1253917B (en:Method)
FR (1) FR1480824A (en:Method)
GB (1) GB1073329A (en:Method)
NL (1) NL149187B (en:Method)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB851113A (en) * 1956-08-02 1960-10-12 Petrochemicals Ltd Improvements in or relating to polymerisation of olefines
US3116274A (en) * 1956-01-18 1963-12-31 Basf Ag Production of olefine polymers
US3180858A (en) * 1961-03-09 1965-04-27 Phillips Petroleum Co Molecular weight control of cis-polyisoprene

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB817308A (en) * 1956-07-02 1959-07-29 Kellogg M W Co Novel catalyst composition, preparation and use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3116274A (en) * 1956-01-18 1963-12-31 Basf Ag Production of olefine polymers
GB851113A (en) * 1956-08-02 1960-10-12 Petrochemicals Ltd Improvements in or relating to polymerisation of olefines
US3180858A (en) * 1961-03-09 1965-04-27 Phillips Petroleum Co Molecular weight control of cis-polyisoprene

Also Published As

Publication number Publication date
FR1480824A (fr) 1967-05-12
NL6606139A (en:Method) 1966-11-25
DE1253917B (de) 1967-11-09
GB1073329A (en) 1967-06-21
BE681438A (en:Method) 1966-10-31
NL149187B (nl) 1976-04-15

Similar Documents

Publication Publication Date Title
US4168357A (en) Preparation of high cis-1,4-polypentadiene
GB2118199A (en) Polymerisation of conjugated dienes
US3549607A (en) High cis polypentenamers
US3459725A (en) High molecular weight unsaturated hydrocarbon homopolymers and process for preparing them
US3165503A (en) Method of polymerizing butadiene-1, 3-hydrocarbons
US3853830A (en) Process for preparing polymers of cyclopentene
EP0002279A1 (en) Process for preparing polymers of cyclopentadiene and bicycloheptene mixtures
US3644585A (en) Process for the preparation of polybutadiene
US3247175A (en) Process for preparing high cis-1, 4-polybutadiene
US3502636A (en) Solution polymerization of isoprene with aluminium trialkyl titanium tetrachloride catalyst activated by ethers and halogenated alkanes
US3458493A (en) Catalyst comprising a nickel component,organometallic,or lialh4 and an arylsubstituted haloalkane or halogen substituted alkene and process for polymerizing 1,3-butadiene therewith
US3635935A (en) Polymerization of ethylene with supported hydrocarbon titanium activated with alkylaluminum
US3448093A (en) Molecular weight control process for polymers
US3317494A (en) Polymerization of conjugated diolefins with a carbon disulfide-containing catalyst
US3644313A (en) Process for polymerizing conjugated dienes
US3317437A (en) Process for the production of alfin catalysts
US3506632A (en) Preparation of plastics
US3423379A (en) Molecular weight control of polymers
US4314045A (en) Polymerization process for cis-1,4-polybutadiene using aliphatic solvents and an aromatic polymerization regulator
US3261821A (en) Process and catalyst for polymerization of 1-olefins
US3462405A (en) Preparation of polymerization catalyst
US3646001A (en) Linear polymers of butadiene
US3923759A (en) Process for the preparation of isobutylene/beta-pinene copolymers
US3639520A (en) Production of butadiene-styrene graft copolymers with a nickel carboxylic acid salt or nickel organic complex compound-titanium tetrachloride-trialkylaluminum catalyst
US3591658A (en) Production of butadiene-styrene graft copolymers with a nickel carboxylic acid salt-boron trifluoride etherate-trialkylaluminum catalyst